Dissociation pathways in low energy (0–2 eV) electron attachment to Cl2O

Dissociative electron attachment (DA) to ClOCl is studied in a high resolution crossed beam experiment. Two complementary ion pairs, Cl−/ClO− and O−/Cl2−, are observed. The Cl−/ClO− pair arises from a simple Cl–OCl bond cleavage with the electron sitting on either of the two fragments. The O−/Cl2− pair is formed by a concerted reaction with the expulsion of O− (or O) and formation of Cl2 (or Cl2−). Ab initio calculations indicate that in low energy electron attachment an electronically excited state of the precursor anion (ClOCl−∗ (2B2)) is involved.